Tetrahydropyranyl- and alkyltetrahydropropyranyl-substituted spiro heterocyclic phosphorus compounds



United States PatentO This invention relates to a novel class oftetrahydropyranyl-substituted spiro heterocyclic vphosphorusconclpounds,and corresponding di'alkyl-and.-te'traalkyltetrahy'dropyranyl-substituted spiro ..heterocy'clicphosphorus compounds.

.The invention also concerns novel processes for the production. of suchcompounds from 'Z-methyloltetrahy-'dropyranyl-tetrahydropyranyl-carbinol and .the corresponding(Z-rnethyloldialkyland tetraalkyltetrahydropyra'nyD- (dialkylandtetraalkyltetrahydropyranyl)-carbinols.

The novel products of the invention have structures apparentlycorresponding to 'the formula:

'WhereinZ isa member of the class consisting of thetetrahydropyran-Z-yl, the 3,4-dialkyland 3,3,4,4-tetraa1kyl-:tetrahydropyran-Lyl, the tetrahydropyran-3-yl, and the 2,4-dialkyland2,2,4,4-tetraalkyltetrahydropyran 3 yl radicals; Z is a radicalof theclass consisting of the The novel products of the invention are made byreacting phosphoryl chloride, phosphoryl bromide, thiophosphorylchloride or phosphorus pentasulfide with a glycol of the structure:

CHzOH whereinZ- and Z haveithe meanings 'hereinbefore indicated. -Suchglycols'are made inwell known manner by dimerizingzacrolein'or abetaalkylor dialkyl-substituted acrolein, followed by the aldolcondensation of the re- 'sultant aldehyde, and subsequent hydrogenationof the unsaturated condensation product. Such processes are described inthe pending application, Serial No. 436,702

- of H. R; Guest and B. W. Kiff, filed June 14, l954, and

in U. S. Patents 2,479,284. and 2,481,377, and British Patent 667,131.

'The products of this invention have'been found tobe useful aspesticides. They likewiseare useful intermediates forathe preparation ofnovel'phosphate esters. For

example,v the: phosphorus ihalides of vthis invention react withalcohols,ialkali;m'etal salts of alc'oholsand phenols, ammoniaandlamines' to: yield neutral esters which are .useful' as plasticizersfor vinyl resins, and as .dyeing assistants, and petroleum additives.

Thedithiophosphorict.acid-derivatives of the invention are usefuliasvulcanization accelerators for rubber,:as promotors in the flotation ofsulfide ores, and oil additives, either as such or in the form ofmetallic salts thereof. Their principal utility .is as intermediates;and they add readily to alpha, beta-olefinically unsaturated compoundsto yield neutral esters that are useful as pesticides, plasticizers forvinyl resins, and as corrosion inhibitors, flotation agents andpetroleum additives.

in the practice of one modification of the'invention for the productionof substituted spiro heterocyclic phosphoryl halides, acompound of thestructure:

CHzOH igK OHOH wherein Z andJZ' have thehereinbeforedescribed'meanings,is'reacted with phosphoryl chloride or phosphoryl bromide attemperatures within the: range: from-10:to 40 C., preferably in.equimolar proportions, although an excess of either reactant canbeuse'd. It'is preferred to add the phosphoryl halide to a solutionof-the diol in an inert solvent such as benzene, although this additioncan be reversed with no deleterious efiect. Theaddition usually is madeWhile maintaining the reaction: mixture at about 25 C. under aroundSOOmm..of mercury pressure. Atmospheric pressure can beused and'thepressure later reduced-to eliminate by-product hydrogen halide. Theresultant product readily can be purified by crystallization from ethylether or other suitable inert solvent, butthis is not necessary unlessan excess of. the diol is used. The product is readily secured inessentially quantitative yield/as a residue product of high purity.

In a modification of the invention=for producing substituted spiroheterocyclic thiophosphoryl halides, a diol of the aforesaid structure:

.GHaOH .z is reacted with thiophosphoryl chloride or thiophosphorylbromide, in the presence of a tertiary amine as a' hydrogen chioridesequestering agent, as illustrated by "the equation:

latented Mar. 18, 1958 V 'halide is added dropwise to an agitatedsolution of an equimolar quantity of the diol and the theoretical amountof tertiary amine in solution in benzene; If desired a benzene solutionof the diol can'be'added to the thiophosphoryl halide in pyridine andbenzene. An excess of either reactant can be employed. The reactionmixture is washed with water to remove the last trace of aminehydrohalide. A substantially pure residue product can be obtained. Ifdesired the latter can be further purified by recrystallization from asuitable solvent such as diethyl ether.

In another modification of the invention for producing substituted spiroheterocyclic dithiophosphoric acids, a diol of the aforesaid structure:

OHzOH is reacted with phosphorus pentasulfide, at temperatures 7 -withinthe range. from 25 to 125 C., although reaction Preferablystoichiometric amounts of the two reactants are employed, but an excessof either reactant can be employed. Preferably the reaction is conductedin the presence of an inert solvent such as benzene, toluene, thexylenes and ethylbenzene, if either the diol reactant or the desiredproduct is a solid. While preferably a toluene solution of the diol isadded'to an agitated suspension of phosphorus pentasulfide' in toluene,the pentasulfide can be added in small successive amounts to theagitated toluene solution of the diol. Y a

The desired product can be crystallized from the reaction mixture whentoluene is used as' solvent. If desired the purification can be elfectedby converting it to the corresponding sodium salt by treatment with anaqueous sodium hydroxide solution, the separation of the aqueous andoily layers thus formed, and the treatment of the aqueous layer with amineral acid such as hydrochloric acid to regenerate the desiredproduct.

The following examples serve to illustrate the 'inven tion.

Example 1 for 44 hours, and finally at 45 C.'under less than 2 mm.

of mercury for one hour, there was obtained spiro [(2- chloro 2 oxo 4tetrahydropyran 2" yl 1,3,2- dioxaphosphorinane) 5,2'-tetrahydropyran]in the form of'618 grams (theory=62l grams) of a solid residue producthaving the following properties: melting point: l45 l50 (3., percentpurity (by esterification) =98.7; analysis (in percent by weight):percent P=9.70 (theory =9.97); percent Cl:l1.04 (theory=l1.42); percentC =46.7O (theory= 46.39); percent H=6.74 (theory=- CH:-() CED-'0 OExample 2 Spiro[(2 chloro 4 tetrahydropyran-2"-yl-2-thiono-1,3,2-dioxaphosphorinane)-5,2-tetrahydropyran] wasprepared by thedropwise addition during 30 minutesfof 16 9 grams (1 mol) ofthiophosphoryl chloride to an agitated solution of 230 grams (1 mol) of2-methyloltetrahydropyran-2-yl-tetrahydropyran- -'yl-carbinol, 15 8grams .(2 mols) of pyridine, and 1000 cc. of benzene, while maintainingthe reaction mixture at 40 C. The mixture then WaS. agitated for 2additional hours at 25 C., and then "stood overnight. The mixture thenwas filtered and the residue (pyridine hydrochloride) washed with ethylether. The combined filtrate and ether washings were neutralized withaconcentrated aqueous sodium bicarbonate solution, washed with200 cc. ofwater, dried over calcium sulfate, filtered, and the filtrate strippedby distillation to a kettle temperature of 25 C. under less than 2 mm.of mercury pressure. The resultant solid was purified by mixing with 800cc. of ethyl ether and filtering. There was thus secured 176 grams ofthe desired product in the form of a white solid residue which, afterair drying, had the-following properties: melting point=146-l56 0;percent purity (by esterification)=97.7; analysis (in percent byweight): percent P=9.55 (theory=9.48); percent Cl=l0.26 (theory=l0.86);percent S=l0.6 (theory-:- 9.81); percent C=43.30 (theory=44.l2); percentH 5.96 (theory=6.l7). The filtrate from the last-named filtration wasstripped by distillation at a kettle temperature of 25 C. under lessthan 2 mm. of mercury pressure and yielded 108 grams of the same solidresidue produc :slightly inferior to that described above.

CHz-O CH2C a while maintaining the reaction mixture at -80 C.-

The mixture was heated for an additional 30 minutes'at C. at which timeevolution of hydrogen sulfide had ceased. The reaction mixture wasfiltered, and the fil trate was stripped by distillation to a kettletemperature of 40 C. under 20 mm. of mercury pressure, cooled to -20 C.,and filtered. The residue from the latter filtration was washed withethyl ether and air dried. There was thus secured 89 grams of theaforesaid spiro com pound in the form of a white solid having thefollowing properties: melting point=l25130 0.; percent purity (byacidity) =98.9%; analysis (percent by weight): per-1 cent 1 :10.46(theory=955); percent S=19.2 (theory-#5 CHz-CH:

uni-o s \H By substituing in the process illustrated by the foregoingexamples for the2-n1ethyloltetrahydropyranr2-yl-tetrahydropyran-2-yl-carbin0lcorresponding. Z-methyldldialkyland tetraalkyl-tetrahydropyran-2yl-dialliyland tetraalkyltetrahydropyran-Z'-yl-carbinols, of the typehereinbefore described, corresponding2-halo-2-0Xo-1,3,2-dioxaphosphorinanes, 2-halo 2thiono-1,3,2-dioXaphosphorinames and2-mercapto-2-thiono-1,3,2-dioxaphosphorinanes areproduced. Preferablyeach alkyl substituent in the tetrahydropyranyl 'ring, when present,contains 1 to 8 carbon atoms. Thus, the reaction of phosphoryl chloridewith 2 methylol-3,4-dialkyltetrahydropyran-2-yl-3',4'dialkyltetrahydropyran-2'-yl carbinol yields spiro{ [2-chloro-4-(3,4"-dialkyltetrahydropyran-Z"-yl )-2-oxo 1,3,2dioxaphosphorinane]-5,2-(3',4' dialkyltetrahydropyran) The following1,3-diols are further illustrative of compounds useful as diol startingmaterials in the practice of the invention:

2methylol-3,4-diethyltetrahydropyran-Z-yl-3-4'-diethyltetrahydropyran-2-yl-carbinolv 2 methylol 3,3,4,4 tetramethyltetrahydropyran-2-yl 3T,3,4',4'-tetramethyltetrahydropyranyl-2'yl-carbinol 2methylol-3,4-di-n-propyltetrahydropyran-2-yl-3',4-din-propyltetrahydropyran-Z'-yl-carbinol2methylol-3,4-dim-butyltetrahydropyran-2-yl-3',4'-di-nbutyltetrahydropyran-2'-yl-carbinol2 methylol-3,4-di-n hexyltetrahydropyran-Z-yl-3,4-di-nhexyltetrahydropyran-2'-yl-carbinol 2methylol-3,4-di-n-pentyltetrahydropyran-2-yl-3',4-di npentyltetrahydropyran-Z-yl-carbinol Z-methylol 3,4di-n-undecyltetrahydropyran-2-yl-3',4'-

di-n-undecyltetrahydropyran-2-yl-carbinol 2methylol-3,4-di-(l-ethylpropyl)-tetrahydropyran-2-yl- 3',4-di-(l-ethylpropyl)-tetrahydropyran-2'-y1 carbinol 2methylol-3,4-di-(1-ethylpentyl)-tetrahydropyran-2-yl-3',4'-dil-ethylpentyl) -tetrahydropyran 2-yl-carbino12-'rnethylol-3,3,4,4 tetra-n-butyltetrahydropyran 2.- yl-3',3',4,4'-tetra n-butyltetrahydropyran-2'-yl-carbinol2-rnethylol-3,3,4,4 tetra-n-hexyltetrahydropyran 2 yl- Z-methylol3,3,4,4-tetra-(2-ethylhexyl)-tetrahydropyran1 2 yl3',3',4,4'-tetra-(2-ethylhexyl) -tetrahydropyran- 2'-yl-carbinol Each ofthese compounds can be reacted with phosphoryl chloride, phosphorylbromide, thiophosphoryl chloride or bromide or phosphorus pentasulfidein accordance with the invention with the production of novel spiroheterocyclic phosphorus compounds of thetype described.

As already indicated, the novel products of this iuvention are usefulpesticides. Thus, the compound of Example 1 is an etfective insecticide,giving a 90-100% kill of red spider mites when used in concentrations aslow as 30 milligrams per 100 cc. of aqueous solution, and giving a90100% kill of bean aphids in 24 hours when used in concentrations ofonly milligrams per 100 cc. of aqueous solution. The compound made inExample 2 is highly effective in giving a 90-100% control of Mexicanbean beetle larvae in 72 hours when used in concentrations of only 7.5milligrams per 100 cc. of aqueous solution.

The invention is susceptible of modification within the scope of theappended claims.

6 I.c1aim: I 1. As new'compoun'ds', tetrahydropyranyl-substituted spiroheterocyclic. phosphorus compounds having structures designated-by theformula uni-0Q I z' c PY (ilH--O 2 wherein Z is a member of the classconsisting of the tetrahydropyran-2 yl, the 3,4-dialkyl.and3,'3,4,4-tetraa1kyltetrahydropyranQ-yl and the tetrahydropyran-3-y1,and 2,4-dialkyland. 2,2,4,4-"tetraalkyltetrahydropyran-3- yl'radicals'wherein each alkyl group contains from l'to llcarbon iatoms; and'ZF is-aradical 'of the class consistin of the CRR'CRR"1CHCH O and radicals,wherein R and R respectively designates a member of the class consistingof hydrogen and the alkyl groups having from 1-to 11 carbon atoms; Xdesignates a member of the class consisting of oxygen and sulfur; Ydesignates a member of the class consisting of chlorine, bromine and theSH" radicals; and Y is SH only when X is S.

2. The product de'fined'in' claim lwherein each alkyl radical presenthas lto Scarbon atoms.

3. As a new compound, spiro' [(2-chloro-2-oxo-4-tetrahydropyran 2" yl1,3,2 dioxaphosphorinane) 5,2 tetrahyd ropyran.

4. As a new compound, spiro [(2-chloro-4-tetrahydropyran 2" yl- 2thiono- 1,3,2- dioxaphosphorina'ne) 5,2' -tetrahydropyran] 5. As a newcompound; spiro [(2 'mercapto-4-tetrahydropyran 2" yl 2 thiono 1,3,2dioxaphosphorinane -5 ,2'-tetrahydr'opyran] 6. Process which comprisesreacting phosphoryl chloride with a glycol of the structure wherein Z isa memberofthe class consisting 'of the tetrahydropyran-2-yl, the3,4-dialkyland 3,3,4,4-tetraalkyltetrahydropyran-2-yl, and thetetrahydropyran-3 -yl, and 2,4-dialkyland2,2,4,4-tetraalkyltetrahydropyran-3- yl radicals wherein each alkylgroup contains from 1 to 11 carbon atoms; and Z is a radical of theclass consisting of the CRR.'CRR'CH CH O- and radicals, wherein R and Rrespectivelydesignate a member of the class consisting of hydrogen andthe alkyl groups having from'l to 11 carbon atoms, in approximatelyequal molar proportions at temperatures within the range from 10 to 40C., in the presence of an inert solvent, and recovering from thereaction mixture the resultant spiro compound of the structure nateschlorine. r 7

groups having from l to, 11 carbon atoms; and W desig- 7.' Process whichcomprises reacting thiophosphoryl chloride with a diol of the structure7 7 V wherein Z is a member of the class consisting of thetetrahydropyran-Z-yl, the 3,4-dialkyland3,3,4,4-tetraalkyltetrahydropyran-Z-yl, and the tetrahydropyran-3-yl,and 2,4-dia1kyland 2,2,4,4-tetraalkyltetrahydropyran-3- yl radicalswherein each alkyl group contains from 1 to 11 carbon atoms; and Z is aradical of the class consisting of the CRRCRR'CH CH O- and V CRROCH CHCRR radicals, wherein Rand R respectively designate a member of theclass consisting of hydrogen and the alkyl groups having from 1 to 11carbon atoms, at temperatures within the range from 25 to 60C. in thepresence of a hydrogen chloride sequestering agent, and in the presenceof an inert diluent, and recovering from the reaction mixradicalswherein R and R, respectively, designate a member of the classconsisting of hydrogen and the alkyl groups having from 1 to 11 carbonatoms; and W designates a member of the class consisting of chlorine.

8. Process which comprises reacting phosphorus pentasulfide attemperatures within the range from 25 125 C., with a diol ofthestructure u wherein Z is a member of the class consisting of thetetrapyran-Z-yl, the 3,4-dia1ky1- and3,3,4,4-tetraalkyltetrahydropyran-Z-yl, and the tetrahydropyran 3-yl,and 2,4-dialkyland 2,2,4,4 tetraalkyltetrahydropyran 3 yl radicalswherein each alkyl group contains from Iii) 11 carbon atoms; and Z is aradical of the class consistin of the CRRCRRCH CH O and Y radicals,wherein R and R respectively designate a member of the classconsisting'of hydrogen and the alkyl groups having from 1 to 11 carbonatoms, in the presence of an inert solvent for the reactants andreaction product,

and recovering from the reaction mixture the resultant spiro compound ofthe structure org-0 s where Z is a member of the class consisting of thetetrahydropyran-Z-yl, the 3,4-dialkyland3,3,4,4-tetraalkyltetrahydropyran-2-yl, and the tetrahydropyran-B-yl,and 2,4-dialkyl and V 2,2,4,4 tetraalkyltetrahydropyran 3 yl radicals;and Z, is a radical of the class consisting of the CRR'CRRCH CH O- and-CRROCH CH CRR radicalswherein R and R, respectively, designate a memberof thejclass consisting of hydrogen and the said alkyl groups. T

9. Process'which comprises reacting a compound of the class consistingof phosphoryl chloride, phosphoryl bromide,rthiophosphoryl chloride;thiophosphoryl bromide and phosphorus'pentasulfide with a glycol .of thestructure a V wherein Z is a member of the class consisting of thetetrahydropyran-2-yl, the, 3,4r-dialkyl-r and3,3,4,4-tetraalkyltetrahydropyran-Z-yl, and the tetrahydropyran-3 yl;and 2,4-dialkyl-, and 2,2,4 ,4-tetraalkyltetrahydropyran-3- yl radicalswherein each alkyl radical has from 1 to 11 carbon atoms; and Z is aradical of the class consisting of the CRRCRRCH CH O and V CRROCH CH CRRradicals, wherein R and R respectively designates a mem ber of the classconsisting of hydrogen and the alkyl groups having from 1 to 11 carbonatoms, in the presence of an inert solvent, and recovering from thereaction mixture the resultant spirocompound of the structure.

wherein Ziis a member of the class consisting of thetetrahydropyran-Z-yl, the 3,4-dialkyland3,3,4,4-tetraalkyltetrahydropyran-Z-yl, and the tetrahydropyran-3-yl,

and 2,4-dialkyland 2,2,4,4-tetraalkyltetrahydropyran-3- yl radicalswhereineach alkyl group contains from 1 to 11, carbonatoms; Z is aradical of the class consisting of the CRRCRRCH CH O and radicalswherein Rand R, respectively, designates a mem-: ber of the classconsisting of hydrogen and thealkyl groups having from 1 to 11 carbonatoms; X designates a member of the class consisting of oxygen andsulfur; Y designates a member of the class consisting of chloride,

' bromide and the SH radicals; and Y is 'SH only whenX isS. p

No-ref erences cited.

1. AS NEW COMPOUNDS, TETRAHYDROPYRANYL-SUBSTITUTED SPIRO HETEROCYCLICPHOSPHORUS COMPOUNDS HAVING STRUCTURES DESIGNATED BY THE FORMULA 9.PROCESS WHICH COMPRISES REACTING A COMPOUND OF THE CLASS CONSISTING OFPHOSPHORYL CHLORIDE, PHOSPHORYL BROMIDE, THIOPHOSPHORYL CHLORIDE,THIOPHOSPHORYL BROMIDE AND PHOSPHORUS PENTASULFIDE WITH A GLYCOL OF THESTRUCTURE